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The thermal carburization of MoO3 nanobelts (nb) and SiO2-supported MoO3 nanosheets under a 1 : 4 mixture of CH4 : H2 yields Mo2C-nb and Mo2C/SiO2. Following this process by in situ Mo K-edge X-ray absorption spectroscopy (XAS) reveals different carburization pathways for unsupported and supported MoO3. In particular, the carburization of α-MoO3-nb proceeds via MoO2, and that of MoO3/SiO2 via the formation of highly dispersed MoOx species. Both Mo2C-nb and Mo2C/SiO2 catalyze the dry reforming of methane (DRM, 800 °C, 8 bar) but their catalytic stability differs. Mo2C-nb shows a stable performance when using a CH4-rich feed (CH4 : CO2 = 4 : 2), however deactivation due to the formation of MoO2 occurs for higher CO2 concentrations (CH4 : CO2 = 4 : 3). In contrast, Mo2C/SiO2 is notably more stable than Mo2C-nb under the CH4 : CO2 = 4 : 3 feed. The influence of the morphology of Mo2C and its dispersion on silica on the structural evolution of the catalysts under DRM is further studied by in situ Mo K-edge XAS. It is found that Mo2C/SiO2 features a higher resistance to oxidation under DRM than the highly crystalline unsupported Mo2C-nb and this correlates with an improved catalytic stability. Lastly, the oxidation of Mo in both Mo2C-nb and Mo2C/SiO2 under DRM conditions in the in situ XAS experiments leads to an increased activity of the competing reverse water gas shift reaction.

Synthesizing high-quality two-dimensional nanomaterials of non-layered metal oxide is a grand challenge because it requires long range single-crystallinity and clean high-energy surfaces. Here, we report the synthesis of single-crystalline MgO(111) nanosheets via a two-step process involving the formation of ultrathin Mg(OH)2 nanosheets as precursor and their selective topotactic conversion upon heating under dynamic vacuum. The defect-rich surface displays terminal -OH groups, 3-coordinated O2- sites, low-coordinated Mg2+ sites as well as single electrons trapped at oxygen vacancies, that render MgO nanosheets highly reactive as evidenced by the activation of CO molecules at low temperatures and pressures, with formation of strongly adsorbed red-shifted CO and coupling of CO molecules into C2 species.

Heterogeneous catalysts in the form of atomically dispersed metals on a support provide the most efficient utilization of the active component, which is especially important for scarce and expensive late transition metals. These catalysts also enable unique opportunities to understand reaction pathways through detailed spectroscopic and computational studies. Here we demonstrate that atomically dispersed iridium sites on indium tin oxide prepared via surface organometallic chemistry display exemplary catalytic activity in one of the most challenging electrochemical processes, oxygen evolution reaction (OER). In situ X-ray absorption studies revealed the formation of IrV=O intermediate under OER conditions with an Ir–O distance of 1.83 Å. Modelling of the reaction mechanism indicates that Ir(V)=O is likely a catalyst resting state, which is subsequently oxidized to Ir(VI) enabling fast water nucleophilic attack and oxygen evolution. We anticipate that the applied strategy can be instrumental in preparing and studying a broad range of atomically dispersed transition metal catalysts on conductive oxides for (photo)electrochemical applications.

LiFePO4 cathode material obtained via solvothermal synthesis was investigated at several charging and discharging stages by a combination of bulk (EELS) and surface sensitive (NEXAFS) methods in order to get insight into the distribution of Li in the surface and bulk region of the particles. Different behavior was observed as a function of the particles morphology. The turbostratic stacking of layers in nanosized crystals induces higher dimensional defects responsible for sluggish Li insertion and extraction within the structure. In contrast, microstructured crystals without higher dimensional defects do not exhibit sluggish Li insertion/extraction, and achieve a higher degree of reversibility during electrochemical cycling.